Semi-crystalline polyolefin-based additive masterbatch composition

ABSTRACT

An additive masterbatch composition comprising a semi-crystalline polyolefin carrier resin and an additive package comprising a product of a reaction of an acidic condensation catalyst and a secondary diarylamine. A moisture-curable polyolefin composition comprising the additive masterbatch composition and a (hydrolyzable silyl group)-functional polyolefin prepolymer. A method of making the compositions; a moisture-cured polyolefin composition prepared therefrom; a manufactured article comprising or made from the formulation; and a method of using the manufactured article.

FIELD

A semi-crystalline polyolefin-based additive masterbatch composition,moisture curable polyolefin compositions prepared therewith, methods ofmaking and using same, and articles containing or made from same.

INTRODUCTION

A masterbatch generally is a solid or liquid additive for impartingcolor (color masterbatch) or other properties (additive masterbatch) toa host material, typically a host polymer. The masterbatch contains acarrier resin and a pigment (color masterbatch) or one or more additives(additive masterbatch). To make a final product, a masterbatch is mixedor blended with a host material to give the final product. Theconcentration of colorant in the color masterbatch and theconcentration(s) of the one or more additives in the additivemasterbatch are typically much higher than target concentration(s)thereof in the final product. To make a polyolefin product, a solidmasterbatch, usually in the form of granules or pellets, is mixed (e.g.,blended) with a solid host polymer, usually in the form of granules orpellets, and the resulting mixture is melted or extruded to make apolyolefin product. Low density polyethylene (LDPE), ethylene/vinylacetate (EVA) copolymer or ethylene/ethyl acrylate (EEA) copolymer istypically used as a carrier resin for solid masterbatches used to makepolyolefin products.

U.S. Pat. No. 6,936,655 B2 to J. S. Borke et al. relates tocrosslinkable flame retardant wire and cable compositions havingimproved abrasion resistance. The compositions are comprised of a highdensity silane-containing polyethylene base resin which can be a blendof a bimodal HDPE and ethylene-silane copolymer or silane-graftedbimodal HDPE in combination with a flame retardant and silanolcondensation catalyst.

EP 2 889 323 A1 to S. Deveci et al. relates to a polymer compositioncomprising carbon black and a carrier polymer for the carbon black. Amasterbatch comprising, preferably consisting of, (I) 20-50 wt % pigmentbased on the total amount of the masterbatch (100 wt %); (II) at least40 wt % of at least one carrier polymer which is a multimodal highdensity polyethylene (HDPE) having an MFR₂ of 1 to 20 g/10 min, adensity of 940 to 965 kg/m³ (pref 950 to 960) and a Mw/Mn of 5.5 to 20;and (IV) optionally further additives.

US 2008/0176981 A1 to M. Biscoglio et al. (BISCOGLIO) relates to amoisture-crosslinkable polymeric composition comprising (a) asilane-functionalized olefinic polymer, (b) an acidic silanolcondensation catalyst, and (c) a secondary-amine-containing antioxidantcomposition. The antioxidant composition can be (1) a secondary aminesubstituted with two aromatic groups or (2) a combination of a firstantioxidant and a secondary amine antioxidant substituted with at leastone aromatic group. The moisture-crosslinkable polymeric composition canbe used for making fibers, films, pipes, foams, and coatings. Thecompositions may be applied as a coating over a wire or a cable.

BISCOGLIO's moisture crosslinkable polymeric composition is preparedfrom a 2-part formulation consisting of an additive package in one partand the (a) silane-functionalized olefinic polymer, such as DFDB-5451ethylene/silane copolymer, in another part [0037]. The additive packagecontains, among other constituents, a blended carrier resin of a lowdensity polyethylene, such as the linear low density polyethyleneDFH-2065, and an ethylene/ethyl acrylate copolymer, such as DPDA-6182,the (b) acidic silanol condensation catalyst, such as a sulfonic acid,and the (c) secondary amine [0037], [0038] and Table 1. The (c)secondary amine may be substituted with two aromatic groups [0005]. TheDFDB-5451 is a host polymer that contains moisture curable silanegroups. The moisture crosslinkable polymeric composition is prepared byextruding the additive package at 5 wt % into the DFDB-5451 [0037]. Themoisture crosslinkable polymeric composition may be cured with watersuch as by exposing the composition at 23° C. and 70% relative humidityfor two days [0039].

SUMMARY

We (the present inventors) have discovered that standard additivemasterbatch compositions that employ carrier resins composed of LDPE orEEA or EVA copolymers suffer from moisture pick-up. Moisture pick-up canlead to premature curing of moisture curable polyolefin compositionsprepared therefrom or decomposition of moisture-sensitive additives.

We conceived a technical solution to this problem that inhibits orprevents moisture pick-up and premature curing of moisture curablepolyolefin compositions and/or decomposition of moisture-sensitiveadditives. The technical solution may also inhibit or prevent phaseseparation or exudation of additive components. The solution includes asemi-crystalline polyolefin-based additive masterbatch composition, aswell as a moisture curable polyolefin composition prepared therewith,methods of making and using same, and articles containing or made fromsame.

DETAILED DESCRIPTION

The Summary and Abstract are incorporated here by reference. Examples ofembodiments include the following numbered aspects.

Aspect 1. An additive masterbatch composition comprising (A) asemi-crystalline polyolefin carrier resin and an additive packagecomprising (B) an acidic condensation catalyst; wherein (A) is 50 to 99weight percent (wt %) and the additive package is from 1 to 50 wt % oftotal weight (100.00 wt %) of the additive masterbatch composition.

Aspect 2. The additive masterbatch composition of aspect 1 wherein the(A) semi-crystalline polyolefin carrier resin consists essentially of,alternatively consists of: (i) a semi-crystalline medium densitypolyethylene; (ii) a semi-crystalline high density polyethylene; (iii) asemi-crystalline polypropylene; (iv) a semi-crystallineethylene/propylene copolymer; (v) a semi-crystallinepoly(ethylene-co-alpha-olefin) copolymer; (vi) a combination (e.g.,mixture or blend) of any two or more of (i), (ii) and (v); (vii) the (A)semi-crystalline polyolefin carrier resin has a crystallinity of 50 to<100 wt %, alternatively 55 to <100 wt %, alternatively 60 to <100 wt %,alternatively 65 to <100 wt %; or (viii) any one of limitations (i) to(vi) and the (A) semi-crystalline polyolefin carrier resin has acrystallinity of 50 to <100 wt %, alternatively 55 to <100 wt %,alternatively 60 to <100 wt %, alternatively 65 to <100 wt %. Aspect 2is any one of (i) to (viii).

Aspect 3. The additive masterbatch composition of aspect 1 or 2 whereinthe (A) semi-crystalline polyolefin carrier resin has (i) a density ofat least 0.925 g/cm³ and is a polyethylene or a density of 0.89 to 0.90g/cm³ and is a polypropylene; (ii) a crystallinity of 50 to <100 wt %and is a polyethylene; (iii) a melt flow index (MFI) of 0.1 to 20 gramsper 10 minutes (g/10 min.) at 190° C./2.16 kg load and is a polyethyleneor a melt flow rate (MFR) of 0.5 to 50 g/10 min. at 230 C./2.16 kg loadand is a polypropylene; (iv) a molecular weight distribution (MWD) thatis monomodal; (v) a MWD that is bimodal; (vi) both (i) and (ii); (vii)both (i) and (iii); (viii) both (ii) and (iii); (ix) both (iv) and atleast one of (i) to (iii); or (x) both (v) and at least one of (i) to(iii). Aspect 3 is any one of (i) to (x).

Aspect 4. The additive masterbatch composition of any one of aspects 1to 3 wherein the (B) acidic condensation catalyst is (i) anorganosulfonic acid, an organophosphonic acid, or a hydrogen halide;(ii) an organosulfonic acid; (iii) an alkyl-substituted arylsulfonicacid; (iv) an alkyl-substituted arylsulfonic acid wherein there is/are 1or 2 (C₅-C₂₀)alkyl substituent(s) and 1 aryl group that is phenyl ornaphthyl; (v) a (C₁-C₅)alkylphosphonic acid, wherein the (C₁-C₅)alkyl isunsubstituted or substituted with one —NH₂ group; (vi) HF, HCl, or HBr;(vii) a Lewis acid; or (viii) a combination of any two or more of (i) to(vii). Aspect 4 is any one of (i) to (viii).

Aspect 5. The additive masterbatch composition of any one of aspects 1to 4 further comprising at least one additive selected from: (C) asecondary diarylamine of formula (I): (R¹—Ar)₂NH (I), wherein each Ar isbenzene-1,4-diyl or both Ar are bonded to each other and taken togetherwith the NH of formula (I) constitute a carbazol-3,6-diyl; and each R¹is independently (C₁-C₂₀)hydrocarbyl; (D) one or two secondantioxidants, each having a structure different than formula (I) andeach other; (E) a processing aid; (F) a colorant; (G) a metaldeactivator; (H) an (unsaturated carbon-carbon bond)-free hydrolyzablesilane; (I) a corrosion inhibitor; (J) a combination of any two or moreof additives (D) to (I); and (K) a product of a reaction of (B) and (C).

Aspect 6. The additive masterbatch composition of aspect 5 furthercomprising the (K) product of a reaction of (B) and (C), wherein: (i)the product of a reaction of (B) and (C) comprises a salt formed by anacid/base reaction of (B) and (C); (ii) the additive package furthercomprises unreacted (B) but not unreacted (C); (iii) the additivepackage further comprises unreacted (C) but not unreacted (B); or (iv)the additive package further comprises unreacted (B) and unreacted (C).Aspect 6 is any one of (i) to (iv). In some aspects at least 50 wt %,alternatively at least 75 wt %, alternatively at least 90 wt % of thecombined weight of (B) and (C) is the product of a reaction of (B) and(C).

Aspect 7. A moisture-curable polyolefin composition comprising theadditive masterbatch composition of any one of aspects 1 to 6 and a(hydrolyzable silyl group)-functional polyolefin prepolymer; wherein inthe (hydrolyzable silyl group)-functional polyolefin prepolymer: (i)each hydrolyzable silyl group is independently a monovalent group offormula (II): (R²)_(m)(R³)_(3-m)Si— (II); wherein subscript m is aninteger of 1, 2, or 3; each R² is independently H, HO—, (C₁-C₆)alkoxy,(C₂-C₆)carboxy, ((C₁-C₆)alkyl)₂N—, (C₁-C₆)alkyl(H)C═NO—, or((C₁-C₆)alkyl)₂C═NO—; and each R³ is independently (C₁-C₆)alkyl orphenyl; (ii) the polyolefin is polyethylene based,poly(ethylene-co-(C₃-C₄₀)alpha-olefin)-based, or a combination thereof;or (iii) both (i) and (ii). Aspect 7 is any one of (i) to (iii).

Aspect 8. A method of making a moisture-curable polyolefin composition,the method comprising mixing a (hydrolyzable silyl group)-functionalpolyolefin prepolymer and a divided solid form of the additivemasterbatch composition of any one of aspects 1 to 6 so as to give amixture; and melting or extruding the mixture so as to make themoisture-curable polyolefin composition.

Aspect 9. A moisture-cured polyolefin composition that is a product ofmoisture curing the moisture curable polyolefin composition of aspect 7,or the composition made by the method of aspect 8, to give themoisture-cured polyolefin composition.

Aspect 10. A manufactured article comprising a shaped form of themoisture-cured polyolefin composition of aspect 9.

Aspect 11. A coated conductor comprising a conductive core and apolymeric layer at least partially surrounding the conductive core,wherein at least a portion of the polymeric layer comprises themoisture-cured polyolefin composition of aspect 9.

Aspect 12. A method of conducting electricity, the method comprisingapplying a voltage across the conductive core of the coated conductor ofaspect 11 so as to generate a flow of electricity through the conductivecore.

Additive masterbatch composition. The additive masterbatch compositionmay contain at least 55 wt %, alternatively at least 70 wt %,alternatively at least 80 wt %, alternatively at least 90 wt % of the(A) semi-crystalline polyolefin carrier resin; all based on total weightof the additive masterbatch composition. The additive masterbatchcomposition may be free of: (i) an ethylene/silane copolymer, (ii) anethylene/vinyl acetate (EVA) copolymer, (iii) an ethylene/alkyl acrylatecopolymer (e.g., EEA copolymer), (iv) carbon black; (v) a pigment orcolorant; (vi) a filler; (vii) a flame retardant; or (viii) any two,alternatively any six of (i) to (vii). The additive masterbatchcomposition may have from >0 to 5 wt % of any other carrier resin,alternatively the additive masterbatch composition may be free of anycarrier resin other than the (A) semi-crystalline polyolefin carrierresin.

The additive masterbatch composition may further comprise the (F)colorant and may be characterized as a color masterbatch composition.The (F) colorant may be a pigment (e.g., carbon black or titaniumdioxide), a dye, or a phosphor; alternatively titanium dioxide or aphosphor. The color masterbatch composition may be free of a HDPE.

The additive masterbatch composition may further comprise a flameretardant and may be characterized as a flame retardant masterbatchcomposition. The flame retardant may be decabromodiphenyl ether;decabromodiphenylethane; a brominated organic polymer; antimony trioxide(a flame retardant synergist); aluminum trihydroxide; magnesiumhydroxide; N,N′-ethylenebis(3,4,5,6-tetrabromophthalimide); a flameretardant silicone; or a combination of any two or more thereof.Examples of the brominated organic polymer are a brominated polystyrene;a brominated rubber a poly(vinyl bromide); a poly(vinylidene bromide); apoly(brominated-alkyl acrylate); a poly(alkyl brominated-acrylate); anda brominated butadiene-styrene copolymer. Examples of the brominatedpolystyrene are poly(4-bromostyrene) and poly(bromostyrene). Examples ofthe brominated rubber are brominated natural rubber and brominatedsynthetic organic rubber. Examples of the poly(brominated-alkylacrylate) are a poly(2-bromoethyl methacrylate) and apoly(2,3-dibromopropyl methacrylate. An example of the poly(alkylbrominated-acrylate) is a poly(methyl-alpha-bromoacrylate). Examples ofthe flame retardant silicone are flame retardant silicone rubber, DOWCORNING 11-100 Additive, and DOW CORNING 4-7081 Resin Modifier.Alternatively the flame retardant masterbatch composition may be free ofa HDPE. A flame retardant synergist is an additive that enhances(increases) flame retarding properties of a mineral flame retardant.Flame retardant synergist are useful as additives in wire and cableinsulation formulations.

The additive masterbatch composition may further comprise a filler andmay be characterized as a filler masterbatch composition. The filler maybe calcium carbonate, zinc borate, zinc molybdate, zinc sulfide, carbonblack, talc, magnesium oxide, zinc oxide, or a clay. Alternatively, thefiller masterbatch composition may be free of a HDPE.

Alternatively, the additive masterbatch composition may be free of (i)(F) colorant, (ii) flame retardant, (iii) filler, (iv) both (i) and(ii), (v) both (i) and (iii), or (vi) both (ii) and (iii).

Constituent (A) semi-crystalline polyolefin carrier resin. Thesemi-crystalline polyolefin carrier resin may be a semi-crystallinepolyethylene that is a semi-crystalline medium density polyethylene(MDPE), a semi-crystalline high density polyethylene (HDPE), or acombination thereof.

The (A) semi-crystalline polyolefin carrier resin may have a density ofat least 0.925 g/cm³, alternatively at least 0.930 g/cm³, alternativelyat least 0.935 g/cm³, alternatively at least 0.940 g/cm³. Thesemi-crystalline HDPE may have a maximum density of 0.970 g/cm³,alternatively at most 0.960 g/cm³, alternatively at most 0.950 g/cm³.The semi-crystalline HDPE may have a density of from 0.930 to 0.970g/cm³, alternatively 0.935 to 0.965 g/cm³. The density of the (A) may bemeasured by ASTM D-1505, Test Method for Density of Plastics by theDensity-Gradient Technique.

The (A) semi-crystalline polyolefin carrier resin may have acrystallinity of at least 55 wt %, alternatively at least 58 wt %,alternatively at least 59 wt %. In any one of the immediately precedingaspects the crystallinity may be at most 90 wt %, alternatively at most80 wt %, alternatively at most 78 wt %. In some aspects thecrystallinity is from 55 to 80 wt %, alternatively from 58 to 78 wt %,alternatively from 58 to 76 wt %, alternatively from 62 to 78 wt %,alternatively any one of 59±1 wt %, 62±1 wt %, 76±1 wt %, and 77±1 wt %.The crystallinity of a semi-crystalline polyolefin resin, such as (A)semi-crystalline polyolefin carrier resin, may be determined bydifferential scanning calorimetry (DSC) according to ASTM D3418-15 orthe Crystallinity Test Method described later. For a semi-crystallinepolyethylene resin, wt % crystallinity=(ΔH_(f)*100%)/292 J/g. For asemi-crystalline polypropylene resin, wt %crystallinity=(ΔH_(f)*100%)/165 J/g. In the respective equations ΔH_(f)is the second heating curve heat of fusion for the polyethylene resin orpolypropylene resin, as the case may be, * indicates mathematicalmultiplication, / indicates mathematical division, 292 J/g is aliterature value of the heat of fusion (ΔH_(f)) for a 100% crystallinepolyethylene, and 165 J/g is a literature value of the heat of fusion(ΔH_(f)) for a 100% crystalline polypropylene. Preferably, crystallinityis determined by DSC according to the Crystallinity Test Methoddescribed later.

The (A) semi-crystalline polyolefin carrier resin may have a melt flowindex (MFI) of 10 to 20 g/10 min., alternatively 0.1 to 10 g/10 min.,alternatively 0.20 to 9 g/10 min. The MFI may be determined by ASTMD1238 (2.16 kilograms (kg), 190° C.)

The (A) semi-crystalline polyolefin carrier resin may be characterizedby a molecular weight distribution (MWD) that is monomodal,alternatively bimodal.

The (A) semi-crystalline polyolefin carrier resin may be asemi-crystalline HDPE that is bimodal and has a density of from 0.950 to0.958 g/cm³ and a MFI of from 0.20 to 0.40 g/10 min. The (A)semi-crystalline polyolefin carrier resin may be a semi-crystalline HDPEthat is monomodal and has a density of from 0.930 to 0.970 g/cm³ and aMFI of from 0.65 to 9 g/10 min., alternatively a density from 0.935 to0.965 g/cm³ and a MFI from 0.7 to 8.5 g/10 min.

Constituent (B) acidic condensation catalyst. The (B) acidiccondensation catalyst is suitable for condensation curing thehydrolyzable silyl groups of the (A) (hydrolyzable silylgroup)-functional polyolefin prepolymer. The (B) may be a Lewis acid,alternatively a Brønsted acid, alternatively a combination of a Lewisacid and a Brønsted acid. As used herein “Lewis acid” means a moleculeor ion that is an electron pair acceptor in neutral water to give apotential of hydrogen (pH) of 6.9 or lower. As used herein “Brønstedacid” means a molecule that is a proton (H⁺) donor in neutral water togive a potential of hydrogen (pH) of 6.9 or lower. In some aspects (B)is any one of Lewis acids (i) to (v): (i) a transition metal-carboxylatecompound or a transition metal-halide compound, wherein the transitionmetal is an element of any one of Groups 3 to 13 of the Periodic Tableof the Elements and each halide is Cl or Br; (ii) the transitionmetal-carboxylate compound; (iii) the transition metal-carboxylatecompound wherein the transition metal is tin, zinc, copper, iron, lead,or titanium; (iv) the transition metal-carboxylate compound wherein eachcarboxylate independently is a (C₁-C₃₀)alkylcarboxylate, alternatively a(C₅-C₃₀)alkylcarboxylate, alternatively a (C₁₀-C₃₀)alkylcarboxylate,alternatively a (C₁₀-C₂₀)alkylcarboxylate, alternatively a(C₁₀-C₁₈)alkylcarboxylate; and (v) dibutyltin dilaurate. Although (B)may be a Lewis acid, typically (B) is a Brønsted acid, such as describedpreviously herein. Constituent (B) may be present in themoisture-curable polyolefin composition at a concentration from 0.01 to0.50 wt %, alternatively at least 0.05 wt %, alternatively at least 0.10wt %; and alternatively at most 0.3 wt %, alternatively at most 0.2 wt%; all based on total weight of the moisture-curable polyolefincomposition. In some aspects (B) is the organosulfonic acid. Examples ofsuitable organosulfonic acids are 4-methylphenylsulfonic acid,dodecylbenzenesulfonic acid, alkylnaphthylsulfonic acids, andorganosulfonic acids in WO 2006/017391; EP 0736065; and U.S. Pat. No.6,441,097.

Constituent (C) secondary diarylamine of formula (I): (R¹—Ar)₂NH (I),wherein Ar and R¹ are as defined above. In some aspects of the (C)secondary diarylamine of formula (I): (i) each Ar is benzene-1,4-diyl;(ii) both Ar are bonded to each other and taken together with the NH offormula (I) constitute a carbazol-3,6-diyl; (iii) each R¹ isindependently (C₁-C₁₀)hydrocarbyl; (iv) each R¹ is independently(C₇-C₂₀)hydrocarbyl; (v) each R¹ is independently benzyl, 1-phenylethyl,or 1-methyl-1-phenylethyl; (vi) 1-methyl-1-phenylethyl; (vii) both (i)and any one of (iii) to (vi); or (viii) both (ii) and any one of (iii)to (vi).

Examples of suitable constituent (C) are 3,6-dibenzylcarbazole;bis(4-benzylphenyl)amine, bis(4-(1-phenylethyl)phenyl)amine, andbis(4-(1-methyl-1-phenylethyl)phenyl)amine. In some aspects of themoisture-curable polyolefin composition, the concentration ofconstituent (C) is greater than, alternatively at least 1.1 times (1.1×)greater than, alternatively at least 1.2× greater than, alternatively atleast 1.3× greater than the concentration of constituent (B). In suchaspects of the moisture-curable polyolefin composition, theconcentration of constituent (C) is less than 1.6×, alternatively lessthan 1.5×, alternatively less than 1.4× the concentration of constituent(B).

Additive (D) one or two second antioxidants, each having a structuredifferent than formula (I) and each other. In some aspects additive (D)is 1 second antioxidant. In other aspects additive (D) is two secondantioxidants. Examples of suitable second antioxidants are polymerized1,2-dihydro-2,2,4-trimethylquinoline (Agerite MA);tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione(Cyanox 1790); distearyl-3,3-thiodiproprionate (DSTDP);tetrakismethylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane(Irganox 1010);1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine (Irganox1024); bis(4,6-dimethylphenyl)isobutylidene (Lowinox 221646); and4,4-thiobis(2-tert-butyl-5-methylphenol) (TBM6).

Additive (E) processing aid. Additive (E) may improve flow of a melt ofthe additive masterbatch composition through a machine. (E) may be anorganic processing aid such as a fluoropolymer or a silicone processingaid such as a polyorganosiloxane or fluoro-functionalizedpolyorganosiloxane. The additive (E) may be used at a concentration offrom 1 to 20 wt %, alternatively 2 to 18 wt %, alternatively 3 to 15 wt%, based on total weight of the additive masterbatch composition.

Additive (F) a colorant. E.g., a pigment or dye. E.g., carbon black ortitanium dioxide. The carbon black may be provided as a carbon blackmasterbatch that is a formulation of poly(l-butene-co-ethylene)copolymer (from 95 wt % to <100 wt % of the total weight of themasterbatch) and carbon black (from >0 wt % to 5 wt % of the totalweight of the masterbatch. The (F) colorant may be from 0.1 to 35 wt %,alternatively 1 to 10 wt %, based on total weight of themoisture-curable polyolefin composition.

Additive (G) a metal deactivator. E.g., oxaylyl bis(benzylidenehydrazide) (OABH). Additive (G) may be from 0.001 to 0.2 wt %,alternatively 0.01 to 0.15 wt %, alternatively 0.01 to 0.10 wt %, allbased on total weight of the moisture-curable polyolefin composition.

Additive (H) (unsaturated carbon-carbon bond)-free hydrolyzable silane.Additive (H) may be any monosilane containing at least 1, alternativelyat least 2, alternatively at least 3, alternatively 4 hydrolyzablegroups (e.g., R² as defined above); and at most 3, alternatively at most2, alternatively at most 1, alternatively 0 non-hydrolyzable(unsaturated carbon-carbon bond)-free groups such as alkyl or arylgroups. Examples of (H) are acetoxytrimethylsilane,4-benzylphenylsulfonoxytributylsilane,dimethylamino-methoxy-dioctylsilane, octyltrimethoxysilane, andtetramethoxysilane. Additive (H) may be from 0.1 to 2 wt %,alternatively 0.1 to 1.5 wt %, alternatively 0.1 to 1.0 wt %; all basedon total weight of the moisture-curable polyolefin composition.

Additive (I) a corrosion inhibitor. E.g., tin (II) sulfate. Additive (I)may be from 0.00001 to 0.1 wt %, alternatively 0.0001 to 0.01 wt %,based on total weight of the moisture-curable polyolefin composition.

The additive masterbatch composition may further comprise otheradditives selected from a lubricant and an anti-blocking agent.

In some aspects the additive masterbatch composition may comprisecarrier resin (A) and an additive package comprising (B) and (C), or aproduct of a reaction of (B) and (C); (D) one or two secondantioxidants; and (G).

Moisture-curable polyolefin composition. The total weight of allconstituents and additives in the moisture-curable polyolefincomposition is 100.00 wt %. The moisture-curable polyolefin compositionmay further comprise water. The additive masterbatch composition may beat a concentration of from 0.1 to 10 wt %, alternatively from 0.5 to 7wt %, alternatively from 1 to 6 wt %, of the moisture-curable polyolefincomposition; all based on total weight of the moisture-curablepolyolefin composition.

The moisture-curable polyolefin composition may be a one-partformulation, alternatively a two-part formulation. The two-partformulation may comprise first and second parts, wherein the first partconsists essentially of a (hydrolyzable silyl group)-functionalpolyolefin prepolymer; wherein the second part consists essentially ofthe additive masterbatch composition.

In some aspects of the moisture-curable polyolefin composition, thedivided solid form of the additive master batch composition may comprisegranules and/or pellets. Prior to the mixing step used to prepare themoisture-curable polyolefin composition, the (hydrolyzable silylgroup)-functional polyolefin prepolymer also may be in a divided solidform (e.g., granules or pellets).

In some aspects of the moisture-curable polyolefin composition, theadditive masterbatch composition may further comprise constituent (C)and the amount of the additive masterbatch composition used may be suchthat the (C), or the ad rem portion of the (K) product of reactionprepared from (B) and (C), is (i) from >0.200 weight percent (wt %) to0.500 wt %; (ii) from 0.220 wt % to 0.500 wt %, (iii) from 0.250 wt % to0.50 wt %, or (iv) from 0.220 wt % to 0.40 wt %; all based on totalweight of the moisture-curable polyolefin composition.

The (hydrolyzable silyl group)-functional polyolefin prepolymer (“HostPolymer”). The polyolefin of the Host Polymer may be polyethylene based,which means that the prepolymer has a backbone formed by polymerizationof ethylene. Alternatively, the Host Polymer may bepoly(ethylene-co-(C₃-C₄₀)alpha-olefin)-based, which means that theprepolymer has a backbone formed by copolymerization of ethylene and atleast one alpha-olefin. Host Polymer may be a reactor copolymer ofethylene and an alkenyl-functional hydrolyzable silane. Thealkenyl-functional hydrolyzable silane may be of formula (III)(R²)_(m)(R³)_(3-m)Si—(C₂-C₆)alkenyl (III), wherein m, R², and R³ are asdefined above for formula (II). The (C₂-C₆)alkenyl may be vinyl, allyl,3-butenyl, or 5-hexenyl. In some aspects the Host Polymer is a reactorcopolymer of ethylene and vinyltrimethoxysilane. Vinyltrimethoxysilaneis an example of the alkenyl-functional hydrolyzable silane of formula(III) wherein subscript m is 3, each R² is a (C₁-C₆)alkoxy, specificallymethoxy; and the (C₂-C₆)alkenyl is vinyl (—C(H)═CH₂). Alternatively,Host Polymer may be a reactor copolymer of ethylene, an alpha-olefin,and the alkenyl-functional hydrolyzable silane, such as in U.S. Pat. No.6,936,671. Alternatively, Host Polymer may be a homopolymer of ethylenehaving a carbon atom backbone having the hydrolyzable silyl groupsgrafted thereonto, such as a polymer made by a process (e.g., a SIOPLAS™process) comprising reactively grafting a hydrolyzable unsaturatedsilane (e.g., vinyltrimethoxysilane) in a post-polymerizationcompounding or extruding step, typically facilitated by a free radicalinitiator such as a dialkyl peroxide, and isolating the resultingsilane-grafted polymer. The grafted polymer may be for used in asubsequent fabricating step. Alternatively, Host Polymer may be acopolymer of ethylene and one or more of (C₃-C₄₀)alpha-olefins andunsaturated carboxylic esters (e.g., (meth)acrylate alkyl esters),wherein the copolymer has a backbone having the hydrolyzable silylgroups grafted thereonto, such as made by a SIOPLAS™ process.Alternatively, Host Polymer may be a mixture of ethylene, a hydrolyzablesilane such as the alkenyl-functional hydrolyzable silane of formula(III), and a peroxide suitable for use in a process (e.g., a MONOSIL™process) comprising reactively grafting a hydrolyzable unsaturatedsilane (e.g., vinyltrimethoxysilane) in a post-polymerizationcompounding or extruding step, typically facilitated by a free radicalinitiator such as a dialkyl peroxide, and using the resultingsilane-grafted polymer immediately (without isolation) in a subsequentfabricating step. Alternatively, Host Polymer may be a mixture of acopolymer of ethylene and one or more of (C₃-C₄₀)alpha-olefins andunsaturated carboxylic esters, a hydrolyzable silane such as thealkenyl-functional hydrolyzable silane of formula (III), and a peroxide,suitable for use in a SIOPLAS™ or MONOSIL™ process. The alpha-olefin maybe a (C₃-C₄₀)alpha-olefin, alternatively a (C₃-C₂₀)alpha-olefin,alternatively a (C₃-C₁₀)alpha-olefin. The alpha-olefin may have at leastfour carbon atoms (i.e., be a (C₄)alpha-olefin or larger). Examples ofthe (C₃-C₁₀)alpha-olefin are propylene, 1-butene, 1-hexene, 1-octene,and 1-decene. The peroxide may be an organic peroxide such as describedin WO 2015/149634 A1, page 5, line 6, to page 6, line 2. The organicperoxide, when present, may be used at a concentration of from 0.02 to 2wt %, alternatively 0.04 to 2 wt %, alternatively 0.04 to 1 wt %,alternatively 0.04 to 0.08 wt %, based on total weight of themoisture-curable polyolefin composition. Host Polymer may be present inthe moisture-curable polyolefin composition at a concentration from 40to 99.78 wt %, alternatively at least 50 wt %, alternatively at least 60wt %; and alternatively at most 99 wt %, alternatively at most 95 wt %,alternatively at most 80 wt %; all based on total weight of themoisture-curable polyolefin composition.

The (hydrolyzable silyl group)-functional polyolefin prepolymer (HostPolymer) may be: (i) a reactor copolymer of ethylene and a hydrolyzablesilane; (ii) a reactor copolymer of ethylene, a hydrolyzable silane, andone or more alpha-olefins and unsaturated carboxylic esters (e.g., U.S.Pat. No. 6,936,671); (iii) a homopolymer of ethylene having a carbonbackbone and a hydrolyzable silane grafted to the carbon backbone (e.g.,made by the SILOPAS™ process); (iv) a copolymer of ethylene, one or morealpha-olefins and unsaturated carboxylic esters, having backbone and ahydrolyzable silane grafted to its backbone (e.g., made by the SILOPAS™process); (v) a copolymer formed from a mixture of ethylene,hydrolyzable silane, and organic peroxide (e.g., made by the MONOSIL™process); or (vi) a copolymer formed from a mixture of ethylene, and oneor more alpha-olefins and unsaturated carboxylic esters, a hydrolyzablesilane, and an organic peroxide (e.g., made by the MONOSIL™ process).

The additive masterbatch and moisture-curable polyolefin compositionsmay be referred to as unfilled compositions when fillers are absenttherefrom. Aspects of the unfilled composition may be made by anysuitable means. For example, an unfilled additive masterbatchcomposition that contains constituents (A) and (B), but does not containfiller, may be made in a Brabender batch mixer by blending theconstituents for 3 minutes at 180° C. melt temperature using cam bladesat 30 rotations per minute (rpm) to give an unfilled melt mixture, andthen allowing the unfilled melt mixture to cool to give the embodimentsof the unfilled composition.

The filler additive masterbatch composition and moisture-curablepolyolefin composition prepared therefrom may be referred to as filledcompositions. Embodiments of the filled compositions may also be made byany suitable means. For example, embodiments of the filled additivemasterbatch composition may be made in a Brabender batch mixer using180° C. melt temperature by first adding the constituents (A) and (B),and optionally (C), into the mixer. Once the constituents (A), (B), and,when present (C), have started melting, then add a filler, andoptionally zero, one or more of additives(s) (D) one or two secondantioxidants, followed by any other additives (E), (F), (G), (H), and/or(I), at flux to give a filled melt mixture. Then homogenize the filledmelt mixture for about 3 minutes, and allow the filled melt mixture tocool to give the embodiments of the filler additive masterbatchcomposition.

Test samples of embodiments of unfilled and filled compositions may beseparately made into compression molded plaques. The mechanicalproperties of these compositions may be characterized using test samplescut from the compression molded plaques.

Any compound herein includes all its isotopic forms, including naturalabundance forms and/or isotopically-enriched forms. Theisotopically-enriched forms may have additional uses, such as medical oranti-counterfeiting applications, wherein detection of theisotopically-enriched form is helpful in treatment or investigation.

The following apply unless indicated otherwise. Alternatively precedes adistinct embodiment. ASTM means the standards organization, ASTMInternational, West Conshohocken, Pa., USA. IEC means the standardsorganization, International Electrotechnical Commission, Geneva,Switzerland. Any comparative example is used for illustration purposesonly and shall not be prior art. Free of or lacks means a completeabsence of; alternatively not detectable. IUPAC is International Unionof Pure and Applied Chemistry (IUPAC Secretariat, Research TrianglePark, N.C., USA). May confers a permitted choice, not an imperative.Operative means functionally capable or effective. Optional(ly) means isabsent (or excluded), alternatively is present (or included). PPM areweight based. Properties are measured using a standard test method andconditions for the measuring (e.g., viscosity: 23° C. and 101.3 kPa).Ranges include endpoints, subranges, and whole and/or fractional valuessubsumed therein, except a range of integers does not include fractionalvalues. Room temperature is 23° C.±1° C. Substituted when referring to acompound means having, in place of hydrogen, one or more substituents,up to and including per substitution.

Advantageously we discovered that the additive masterbatch compositionis slow to pick up moisture. Thus, the additive masterbatch compositionmay have a shelf-life that is longer than a comparative composition thatdoes not contain (A) before it is used to prepare the moisture-curablepolyolefin composition. The additive masterbatch composition inhibits orprevents moisture pick-up and premature curing of moisture curablepolyolefin compositions and/or decomposition of moisture-sensitiveadditives. The additive masterbatch composition may also inhibit orprevent phase separation or exudation of additive components. Themoisture-cured polyolefin composition has satisfactory extent ofcrosslinking and has good heat aging performance under several differenttest conditions. Also, the moisture-cured polyolefin composition hasgood mechanical properties such as tensile strength andelongation-at-break. These characteristics make the moisture-curedpolyolefin composition useful in a variety of applications including asa component of a coating of a coated conductor such as a coated wire orcoated cable.

Additive Masterbatch Composition Preparation Methods 1 to 3. Melt blendconstituents of the additive masterbatch compositions (of comparativeand inventive examples) either Method 1 in a Banbury compounder using acompounding temperature of 155° C., rotor speed of 60 to 65 rotationsper minute (rpm) or Method 2 in a ZKS twin-screw extruder using anextrusion temperature of 160° C. and a screw speed of 200 rpm or Method3 in a Brabender compounder using a compounding temperature of 150° C.and rotor speed of 30 rpm. All resulting additive masterbatchcompositions were dried at 70° C. for 24 hours before being used toprepare coated conductors.

Crystallinity Test Method. For determining crystallinity in wt % of asemi-crystalline polyolefin resin such as (A) semi-crystallinepolyolefin carrier resin. Determine melting peaks and weight percent (wt%) crystallinity using DSC instrument DSC Q1000 (TA Instruments) asfollows. (A) Baseline calibrate instrument. Use software calibrationwizard. First obtain a baseline by heating a cell from −80° to 280° C.without any sample in an aluminum DSC pan. Then use sapphire standardsas instructed by the calibration wizard. The analyze 1 to 2 milligrams(mg) of a fresh indium sample by heating the standards sample to 180°C., cooling to 120° C. at a cooling rate of 10° C./minute, then keepingthe standards sample isothermally at 120° C. for 1 minute, followed byheating the standards sample from 120° to 180° C. at a heating rate of10° C./minute. Determine that indium standards sample has heat of fusion(H_(f))=28.71±0.50 Joules per gram (J/g) and onset ofmelting=156.6°±0.5° C. Perform DSC measurements on test samples usingsame DSC instrument. For polyethylene test samples see procedure (B)below. For polypropylene test samples see procedure (C) below.

(B) DSC on Polyethylene Test Samples. Press test sample of polymer intoa thin film at a temperature of 160° C. Weigh 5 to 8 mg of test samplefilm in DSC pan. Crimp lid on pan to seal pan and ensure closedatmosphere. Place sealed pan in DSC cell, equilibrate cell at 30° C.,and heat at a rate of about 100° C./minute to 140° C., keep sample at140° C. for 1 minute, cool sample at a rate of 10° C./minute to 0° C. orlower (e.g., −40° C.) to obtain a cool curve heat of fusion (H_(f)), andkeep isothermally at 0° C. or lower (e.g., −40° C.) for 3 minutes. Thenheat sample again at a rate of 10° C./minute to 180° C. to obtain asecond heating curve heat of fusion (ΔH_(f)). Using the resultingcurves, calculate the cool curve heat of fusion (J/g) by integratingfrom the beginning of crystallization to 10° C. Calculate the secondheating curve heat of fusion (J/g) by integrating from 10° C. to the endof melting. Measure weight percent crystallinity (wt % crystallinity) ofthe polymer from the test sample's second heating curve heat of fusion(ΔH_(f)) and its normalization to the heat of fusion of 100% crystallinepolyethylene, where wt % crystallinity=(ΔH_(f)*100%)/292 J/g, whereinΔH_(f) is as defined above, * indicates mathematical multiplication, /indicates mathematical division, and 292 J/g is a literature value ofheat of fusion (ΔH_(f)) for a 100% crystalline polyethylene.

(C) DSC on Polypropylene Test Samples. Press test sample ofpolypropylene into a thin film at a temperature of 210° C. Weigh 5 to 8mg of test sample film in DSC pan. Crimp lid on pan to seal pan andensure closed atmosphere. Place sealed pan in DSC cell and heat at arate of about 100° C./minute to 230° C., keep sample at 230° C. for 5minutes, cool sample at a rate of 10° C./minute to −20° C. to obtain acool curve heat of fusion, and keep isothermally at −20° C. for 5minutes. Then heat sample again at a rate of 10° C./minute until meltingis complete to obtain a second heating curve heat of fusion ((ΔH_(f))).Using the resulting curves, calculate the cool curve heat of fusion(J/g) by integrating from the beginning of crystallization to 10° C.Calculate the second heating curve heat of fusion (J/g) by integratingfrom 10° C. to the end of melting. Measure weight percent crystallinity(wt % crystallinity) of the polymer from the test sample's secondheating curve heat of fusion (ΔH_(f)) and its normalization to the heatof fusion of 100% crystalline polypropylene, where wt %crystallinity=(ΔH_(f)*100%)/165 J/g, wherein ΔH_(f) is as definedabove, * indicates mathematical multiplication, / indicates mathematicaldivision, and 165 J/g is a literature value of heat of fusion (ΔH_(f))for a 100% crystalline polypropylene.

In other aspects the crystallinity is at room temperature of thesemi-crystalline polyolefin (e.g., the semi-crystalline medium densitypolyethylene, semi-crystalline high density polyethylene, or thesemi-crystalline poly(ethylene-co-alpha-olefin) copolymer (collectively“semi-crystalline ethylenic (co) polymer”)) and is calculated using thefollowing equation.

${{{Wt}\mspace{14mu}\%\mspace{14mu}{crystallinity}} = {\frac{\rho_{c}}{\rho}\left( \frac{\rho - \rho_{a}}{\rho_{c} - \rho_{a}} \right)}},$

Baseline calibration of DSC instrument. Use software calibration wizard.First obtain a baseline by heating a cell from −80° to 280° C. withoutany sample in an aluminum DSC pan. Then use sapphire standards asinstructed by the calibration wizard. Then analyze 1 to 2 milligrams(mg) of a fresh indium sample by heating the standards sample to 180°C., cooling to 120° C. at a cooling rate of 10° C./minute, then keepingthe standards sample isothermally at 120° C. for 1 minute, followed byheating the standards sample from 120° to 180° C. at a heating rate of10° C./minute. Determine that indium standards sample has heat offusion=28.71±0.50 Joules per gram (J/g) and onset of melting=156.6°±0.5°C.

Perform DSC measurements on test samples using same DSC instrument.Press test sample of semi-crystalline ethylenic (co) polymer into a thinfilm at a temperature of 160° C. Weigh 5 to 8 mg of test sample film inDSC pan. Crimp lid on pan to seal pan and ensure closed atmosphere.Place sealed pan in DSC cell, equilibrate cell at 30° C., and heat at arate of about 100° C./minute to 190° C. Keep sample at 190° C. for 3minutes, cool sample at a rate of 10° C./minute to −60° C. to obtain acool curve heat of fusion (Hf), and keep isothermally at −60° C. for 3minutes. Then reheat sample at a rate of 10° C./minute to 190° C. toobtain a second heating curve heat of fusion (ΔHf). Using the secondheating curve, calculate the “total” heat of fusion (J/g) by integratingfrom −20° C. (in the case of semi-crystalline ethylenic (co) polymersexcept poly(ethylene-co-alpha-olefin) copolymers of density greater thanor equal to 0.90 g/cm³) or −40° C. (in the case ofpoly(ethylene-co-alpha-olefin) copolymers of density less than 0.90g/cm³) to end of melting. Using the second heating curve, calculate the“room temperature” heat of fusion (J/g) from 23° C. (room temperature)to end of melting by dropping perpendicular at 23° C. Measure and report“total crystallinity” (computed from “total” heat of fusion) as well as“crystallinity at room temperature” (computed from “room temperature”heat of fusion). Crystallinity is measured and reported as percent (%)or weight percent (wt %) crystallinity from the test sample's secondheating curve heat of fusion (ΔHf) and its normalization to the heat offusion of 100% crystalline polyethylene, where % crystallinity or wt %crystallinity=(ΔHf*100%)/292 J/g, wherein ΔHf is as defined above, *indicates mathematical multiplication, / indicates mathematicaldivision, and 292 J/g is a literature value of heat of fusion (ΔHf) fora 100% crystalline polyethylene.

Elongation-at-Break Test Method. Measured on 5 inches (12.7 centimeter(cm)) long, fully moisture-cured test samples, prepared according to theMoisture Curing Test Method described below, using an Instron machineand 10 inches per minute (25.4 cm per minute) according to IEC 60502,and expressed as a percent. Minimum value per IEC 60502 specificationsis 200%.

Heat Aging Performance Test Method (HEPTM) 1: oxidative induction time(OIT). Measures the time required to initiate oxidation of a test sampleof the moisture-cured polyolefin composition, prepared by the belowMoisture Curing Test Method, under molecular oxygen when temperature isincreased at a rate of 10° C. per minute in a differential scanningcalorimeter (DSC). Record the time in minutes until oxidative inductionis detected. Oxidative induction time is determined by heating a testsample up from 25° C. at a heating rate of 10° C./min., and observingthe time of onset of oxidation by detecting the beginning of oxidationas an exothermic peak in differential scanning calorimetry (DSC). Thelonger the time in minutes for OIT, the more resistant to oxidative heataging the test sample. HEPTM 1 is preferred over HEPTM 2 and 3 inassessing overall heat aging performance. In some aspects themoisture-cured polyolefin composition has an OIT according to HEPTM 1 ofat least 40 minutes, alternatively at least 45 minutes, alternatively atleast 60 minutes.

Heat Aging Performance Test Method (HEPTM) 2: heat aging withoutconductor. Place test sample of the moisture-cured polyolefincomposition, prepared by the below Moisture Curing Test Method, in anoven at 135° C. for 168 hours according to IEC 60502. Remove theresulting heat-aged test sample from the oven, and allow it to cool for16 hours at room temperature. Assess elongation-at-break and tensilestrength of the heat-aged test samples according to their respectiveTest Methods described herein, and compare the results toelongation-at-break and tensile strength of the test samples prior toheat aging. If the difference in elongation-at-break and tensilestrength of the heat-aged test sample is less than 25% of theelongation-at-break and tensile strength of the test sample prior toheat aging, the test sample passes HAPTM 2. If the difference is greaterthan 25%, the test sample fails HAPTM 2. In some aspects themoisture-cured polyolefin composition passes at least the tensilestrength test, alternatively at least the elongation-at-break test,alternatively both (T&E) according to HEPTM 2.

Heat Aging Performance Test Method (HEPTM) 3: heating aging on copperconductor using Mandrel bend test. Heat age a coated conductor, preparedaccording to the Moisture Curing Test Method described below wherein the14 AWG conductor is a copper wire, at 150° C. for 10 days, and allowingthe heat aged coated conductors to cool to room temperature for 16 hoursto give cooled, heat-aged coated conductors. IEC-60502-1 specifies thatif after such heat aging it is difficult to remove the coating from theconductor without compromising it, then perform a Mandrel bend test. Inthe Mandrel bend test, wind the cooled, heat-aged coated conductorsaround a mandrel at a rate of 1 turn every 5 seconds. The diameter ofthe mandrel and number of turns are based on the thickness of the copperconductor, as specified by IEC-60502-1. If after winding there is nocrack in the coating, the coated conductor passes this test. If there iscracking in the coating of the coated conductor after winding, thecoated conductor fails. In some aspects the moisture-cured polyolefincomposition passes HEPTM 3.

Hot Creep Test Method. Measures extent of crosslinking, and thus extentof curing, in the test sample of the moisture-cured polyolefincomposition prepared by the below Moisture Curing Test Method. Removethe moisture-cured polyolefin composition from the coated wires preparedby the Moisture Curing Test Method, measure its initial length, andsubject the measured test sample to hot creep test conditions comprisinga load of 20 Newtons per square meter (N/m²) at 200° C. for 15 minutesto give a tested sample. Remove the tested sample from the hot creeptest conditions, cool and measure the length of the tested sample.Express the extent of elongation of the test sample as a percentage (%)of the length of the tested sample after hot creep conditions relativeto the initial length of test sample prior to hot creep conditions. Thelower the hot creep percent, the lower the extent of elongation of atest sample under load, and thus the greater the extent of crosslinking,and thus the greater the extent of curing. In some aspects themoisture-cured polyolefin composition has a hot creep according to HotCreep Test Method of <30%, alternatively 25%, alternatively 23%; andalternatively at least 15%, alternatively at least 16%, alternatively atleast 18%.

Moisture Curing Test Method. Cures the moisture curable polyolefincomposition. Moisture curing may be performed for testing purposesaccording to the following procedure. Soak 95 wt % of Part 1 and 5 wt %of Part 2. Part 1 is a mixture of 0.5 wt % octyltrimethoxysilane and99.5 wt % of (hydrolyzable silyl group)-functional polyolefin prepolymer1 described later (a reactor copolymer of 98.5 wt % ethylene and 1.5 wt% vinyltrimethoxysilane), wherein prepolymer 1 has been soaked with theoctyltrimethoxysilane to give the mixture of Part 1. Part 2 is anembodiment of the additive masterbatch composition, and, if present, oneor more of additives (D) to (H). Combine Parts 1 and 2 in a wirelineextruder to form 25 mils (0.635 millimeter (mm)) thick wall wires with14 AWG conductors. Place the resulting coated wires in a water bath at90° C. for three hours, and then remove the coated wires to give anaspect of the coated conductor having a coating comprising an aspect ofthe moisture-cured polyolefin composition. Remove the moisture-curedpolyolefin composition from the coated wires and measure extent ofcrosslinking by the Hot Creep Test Method, wherein the lower the extentof elongation the higher the extent of crosslinking, and thus the lowerthe Hot Creep %. Remove other samples of the moisture-cured polyolefincomposition from the coated wires and measure tensile strength andelongation-at-break according to the respective test methods describedherein. Test other samples of the moisture-cured polyolefin compositionremoved from the coated wires using HEPTM 1 (oxidative induction time orOIT), and HEPTM 3 (heating aging on copper conductor using Mandrel bendtest).

Moisture Pick-Up Test Method. Measure moisture content of a test sample(Time 0). Then place the test sample in 70% relative humidity at roomtemperature for 48 hours, and measure moisture content in parts permillion (ppm) after 2.5, 4, 21, and 48 hours or after 0, 2, 4, 8, 24,and 48 hours.

Tensile Strength Test Method. Measured on 5 inches (12.7 centimeters(cm)) long, fully moisture-cured test samples, prepared according to theMoisture Curing Test Method described above, using an Instron machineand 10 inches per minute (25.4 cm per minute) according to IEC 60502,and expressed as pounds per square inch (psi). Minimum value per IEC60502 specifications is 1,800 psi (12,000 kilopascals (kPa)).

EXAMPLES

Comparative carrier resin 1 (CCR1): a linear low density polyethylene(LLDPE) having a density of 0.920 g/cm³, a melt flow index of 0.55 to0.75 g/10 min., and a monomodal MWD. By the Crystallinity Test Methodparts (A) and (B), CCR1 had a second heating curve heat of fusion(ΔH_(f)) of 135.1 J/g, and a corresponding crystallinity of 46.3 wt %.Available as product DFH-2065 from The Dow Chemical Company, Midland,Mich., USA.

Comparative carrier resin 2 (CCR2): an ethylene/ethyl acrylate copolymerhaving a melt flow index from 1.0 to 1.6 g/10 min. and a monomodal MWD.By the Crystallinity Test Method parts (A) and (B), CCR2 had a secondheating curve heat of fusion (ΔH_(f)) of 84.2 J/g, and a correspondingcrystallinity of 28.8 wt %. Available as product AMPLIFY™ EA 100Functional Polymer from The Dow Chemical Company.

Comparative carrier resin 3 (CCR3): low density polyethylene (LDPE)having a melt flow index 2 g/10 min. and density of 0.92 g/cm³ and amonomodal MWD. By the Crystallinity Test Method parts (A) and (B), CCR3had a second heating curve heat of fusion (ΔH_(f)) of 133.7 J/g, and acorresponding crystallinity of 45.8 wt %. Available as product DXM-487from The Dow Chemical Company.

Comparative carrier resin 4 (CCR4): low density polyethylene (LDPE)having a melt flow index 2.35 g/10 min. and density of 0.922 g/cm³ and amonomodal MWD. By the Crystallinity Test Method parts (A) and (B), CCR4had a second heating curve heat of fusion (ΔH_(f)) of 131.2 J/g, and acorresponding crystallinity of 44.9 wt %. Available as product DXM-446from The Dow Chemical Company.

Comparative carrier resin 5 (CCR5): a linear low density polyethylene(LLDPE) having a melt flow index of 0.65 g/10 min., a density of 0.92g/cm³, and a monomodal MWD. By the Crystallinity Test Method parts (A)and (B), CCR5 had a second heating curve heat of fusion (ΔH_(f)) of128.2 J/g, and a corresponding crystallinity of 43.9 wt %. Available asproduct DFH-2065 from The Dow Chemical Company, Midland, Mich., USA.

Constituent (A1) semi-crystalline polyolefin carrier resin 1: a HDPEhaving a density of 0.965 g/cc³, a melt flow index of 7.5 to 8.5 g/10min.; and a monomodal MWD. By the Crystallinity Test Method parts (A)and (B), (A1) had a second heating curve heat of fusion (ΔH_(f)) of223.7 J/g, and a corresponding crystallinity of 76.6 wt %. Available asproduct DGDA-6944 NT from The Dow Chemical Company.

Constituent (A2) semi-crystalline polyolefin carrier resin 2: a HDPEhaving a density of 0.9545 g/cc³, a melt flow index of 0.22 to 0.38 g/10min.; and a bimodal MWD. By the Crystallinity Test Method parts (A) and(B), (A2) had a second heating curve heat of fusion (ΔH_(f)) of 222.2J/g, and a corresponding crystallinity of 76.1 wt %. Available asproduct DGDA-1310 NT from The Dow Chemical Company.

Constituent (A3) semi-crystalline polyolefin carrier resin 3: a HDPEhaving a density of 0.955 g/cc³, a melt flow index of 1.2 to 1.8 g/10min.; and a monomodal MWD. By the Crystallinity Test Method parts (A)and (B), (A3) has a second heating curve heat of fusion (ΔH_(f)) of181.1 J/g, and a corresponding crystallinity of 62.0 wt % (based on datafor product DMDA-1250). Available as product DGDA-1250 NT from The DowChemical Company.

Constituent (A4) semi-crystalline polyolefin carrier resin 4: a HDPEhaving a density of 0.944 g/cc³, a melt flow index of 0.87 to 1.07 g/10min.; and a monomodal MWD. Crystallinity Test Method data unavailablebut expect crystallinity from >50 to <100 wt %. Available as productDGDA-4593 NT from The Dow Chemical Company.

Constituent (A5) semi-crystalline polyolefin carrier resin 5: a HDPEhaving a density of 0.935 g/cc³, a melt flow index of 0.7 to 0.9 g/10min.; and a monomodal MWD. By the Crystallinity Test Method parts (A)and (B), (A5) had a second heating curve heat of fusion (ΔH_(f)) of171.2 J/g, and a corresponding crystallinity of 58.6 wt %. Available asproduct DGDA-3580 NT from The Dow Chemical Company.

Constituent (A6) semi-crystalline polyolefin carrier resin 6: a HDPEhaving a density of 0.955 g/cc³, a melt flow index of 1.2 to 1.8 g/10min.; and a monomodal MWD. By the Crystallinity Test Method parts (A)and (B), (A6) has a second heating curve heat of fusion (ΔH_(f)) of181.1 J/g, and a corresponding crystallinity of 62.0 wt % (based on datafor product DMDC-1250). Available as product DGDC-1250 from The DowChemical Company.

Constituent (B1): an alkyl-substituted naphthylsulfonic acid (NacureCD-2180).

Constituent (B2): dibutyltin dilaurate

Constituent (C1): bis(4-(1-methyl-1-phenylethyl)phenyl)amine (Naugard445).

Additive (D1): bis(4,6-dimethylphenyl)isobutylidene (Lowinox 221646).

Additive (D2): distearyl-3,3-thiodiproprionate (DSTDP).

Additive (D3): tetrakismethylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane (IRGANOX-1010 FF).

Additive (G1): oxaylyl bis(benzylidene hydrazide) (OABH).

Additive MB-2000: a low density polyethylene/antioxidant masterbatchcontaining 20 wt % of1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine asantioxidant and 80 wt % of LDPE as carrier resin.1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine is availableas Irganox 1024.

(Hydrolyzable silyl group)-functional polyolefin prepolymer 1 (HostPolymer 1): reactor copolymer of 98.5 wt % ethylene and 1.5 wt %vinyltrimethoxysilane. Prepared by copolymerizing ethylene andvinyltrimethoxysilane in a tubular high pressure polyethylene reactorwith a free radical initiator. Available as DFDA-5451 from The DowChemical Company.

(Hydrolyzable silyl group)-functional polyolefin prepolymer 2 (HostPolymer 2): 99.5 wt % Host Polymer 1 and 0.5 wt % octyltriethoxysilane(as moisture scavenger) made by soaking the octyltriethoxysilane intothe Host Polymer 1.

Comparative Examples 1 and 2 (CE1 & CE2): comparative additivemasterbatch compositions. See compositions and stickiness test resultsdescribed in Tables 1 and 2 later.

Inventive Examples 1 to 5 (IE1 to IE5): inventive additive masterbatchcompositions. See compositions and stickiness test results described inTables 1 and 2 below.

TABLE 1 Compositions of CE1, CE2 and IE1 to IE5. Ex. No. CE1 CE2 IE1 IE2IE3 IE4 IE5 CCR1 44.97 None None None None None None CCR2 44.97 44.97None None None None None (A1) wt % None 44.97 89.94 None None None None(A2) wt % None None None 89.94 None None None (A3) wt % None None NoneNone 89.94 None None (A4) wt % None None None None None 89.94 None (A5)wt % None None None None None None 89.94 (B1) wt % 4 4 4 4 4 4 4 (C1) wt% 3.3 3.3 3.3 3.3 3.3 3.3 3.3 (D1) wt % 1 1 1 1 1 1 1 (D2) wt % 1 1 1 11 1 1 (G1) wt % 0.76 0.76 0.76 0.76 0.76 0.76 0.76 Total wt % 100 100100 100 100 100 100

TABLE 2 Moisture Pick-Up of CE1, CE2 and IE1 to IE5. Ex. No. CE1 CE2 IE1IE2 IE3 IE4 IE5 Time 0 75 ppm 30 ppm 28 ppm 29 ppm 18 ppm 11 ppm 20 ppm2.5 hours 192 ppm 154 ppm 71 ppm 75 ppm Not test. 38 ppm 70 ppm 4 hours260 ppm 178 ppm 81 ppm 93 ppm 75 ppm 61 ppm 94 ppm 21 hours 383 ppm 253ppm 81 ppm 79 ppm 109 ppm Not test. 70 ppm 48 hours 490 ppm 302 ppm 142ppm 155 ppm 125 ppm 92 ppm 121 ppm

Moisture pick-up data in Table 2 show that the comparative additivemasterbatch compositions, based on carrier resin that is LLDPE/EEA orEEA/HDPE, started with a higher moisture (H₂O) content (Time 0), and hada substantially higher moisture content after 48 hours exposure thereto.In beneficial contrast, the inventive additive masterbatch compositionsof IE1 to IE5, based on semi-crystalline HDPE carrier resin, startedwith a much lower moisture content and had a much lower moisture contentafter 48 hours.

Comparative Examples A1 and A2 and Inventive Examples A1 to A5:comparative and inventive moisture-curable polyolefin compositions andmoisture-cured polyolefin compositions prepared therefrom by curingsame. Follow Moisture Curing Test Method using 5 wt % additivemasterbatch compositions of CE1, CE2 and IE1 to IE5, respectively, and95 wt % of the Host Polymer 1 to give moisture-curable polyolefincompositions of CEA1, CEA2, and IEA1 to IEA5, respectively. Cure thesecurable compositions to give moisture-cured polyolefin compositions ofCEA1, CEA2, and IEA1 to IEA5, respectively. Test these moisture curedcompositions using Heat Aging Performance Test Method (HEPTM) 1:oxidative induction time reported in minutes (“OIT (min.)”) and HeatAging Performance Test Method (HEPTM) 3: heating aging on copperconductor using Mandrel bend test reported as pass or fail (“Mandrel(P/F)”). Measure second heating curve heat of fusion (ΔH_(f)) anddetermine crystallinity according to the Crystallinity Test Method parts(A) and (B). Results are reported below in Table 3.

TABLE 3 Heat aging performance of moisture-cured polyolefincompositions. Ex. No. CEA1 CEA2 IEA1 IEA2 IEA3 IEA4 IEA5 Host Polymer 195 wt % 95 wt % 95 wt % 95 wt % 95 wt % 95 wt % 95 wt % Additive MB Ex.CE1 CE2 IE1 IE2 IE3 IE4 IE5  5 wt %  5 wt %  5 wt %  5 wt %  5 wt %  5wt %  5 wt % OIT at 200° C. (min.) 67.3 Not Tested 58.4 76.5 Not Tested76.1 Not Tested Mandrel (P/F) Pass Pass Pass Pass Pass Pass Pass

Heat aging performance data in Table 3 show that the moisture-curedpolyolefin compositions of inventive examples (IEA1 to IEA5) made frommoisture-curable polyolefin compositions prepared using the inventiveadditive masterbatch (MB) compositions IE1 to IE5, respectively, havecomparable heat aging performance as the moisture-cured polyolefincompositions comparative examples CEA1 and CEA2 made frommoisture-curable polyolefin compositions prepared using comparativeadditive masterbatch (MB) compositions CE1 and CE2, respectively. Theinventive additive masterbatch compositions having a carrier resinconsisting essentially of semi-crystalline HDPE heat age as well ascomparative additive masterbatch compositions having a carrier resinconsisting essentially a blend of LLDPE and EEA (CEA1) or a blend of EEAand HDPE (CEA2). Table 2 data show the semi-crystalline polyolefincarrier resin of the inventive additive masterbatch compositions iseffective (as good as EEA and LLDPE) at delivering antioxidants to thehost resin, and show that the inventive moisture-cured polyolefincompositions (e.g., of IEA1 to IEA2) have the performance that make themuseful in a variety of applications including as a component of acoating of a coated conductor such as a coated wire or coated cable.

Incorporate by reference here the below claims as numbered aspectsexcept replace “claim” and “claims” by “aspect” or “aspects,”respectively.

Comparative Examples 3 and 4 (CE3 & CE4): comparative additivemasterbatch compositions. See compositions and stickiness test resultsdescribed in Tables 4 and 5 later.

Inventive Examples 6 and 7 (IE6 and IE7): inventive additive masterbatchcompositions. See compositions and stickiness test results described inTables 4 and 5 below.

TABLE 4 Compositions of CE3, CE4, IE6 and IE7 (0 = 0.00). Ex. No. CE3CE4 IE6 IE7 CCR3 wt % 73.3 0 0 0 CCR4 wt % 13.32 0 0 0 CCR5 wt % 0 85.720 0 (A6) wt % 0 0 86.62 0 (A1) wt % 0 0 0 86.62 (B2) wt % 1.7 2.6 1.72.6 (D3) wt % 3.33 3.33 3.33 3.33 MB-2000 wt % 8.35 8.35 8.35 8.35 Totalwt % 100 100 100 100

TABLE 5 Moisture Pick-Up of CE1, CE2 and IE1 to IE5. Ex. No. CE3 CE4 IE6IE7 Time 0 75 ppm 51.9 ppm 53 ppm 42.1 ppm 2 hours 118 ppm 79.5 ppm 45.1ppm 56.3 ppm 4 hours 178 ppm 117 ppm 84.2 ppm 84.4 ppm 8 hours 268 231120.3 137 24 hours 319 ppm 247 ppm 198 ppm 260.3 ppm 48 hours 305 ppm278 ppm 211 ppm 237 ppm

Moisture pick-up data in Table 5 show that the comparative additivemasterbatch compositions, based on carrier resin that is LDPE or LLDPE,had a substantially higher moisture content after 2, 4, 8 and 48 hoursexposure thereto. In beneficial contrast, the inventive additivemasterbatch compositions of IE6 and IE7, based on semi-crystalline HDPEcarrier resin, had much lower moisture contents after 2, 4, 8, and 48hours. Further, both CE3 and IE6 had the same amounts of additivesMB-2000, (D3), and (B2), and yet IE6 had lower initial moisture contentat Time 0 (0 hour) than CE3. Similarly, both CE4 and IE7 had the sameamounts of additives MB-2000, (D3), and (B2), and yet IE7 had lowerinitial moisture content at Time 0 (0 hour) than CE4. Thus it can beconcluded from the data that the inventive moisture-curable polyolefincomposition comprising the inventive additive masterbatch will havelower moisture pickup and thus greater resistance to scorch (prematurecuring) compared to a comparative moisture-curable polyolefincomposition comprising a comparative additive masterbatch composition.

The invention claimed is:
 1. An additive masterbatch compositioncomprising (A) a semi-crystalline polyolefin carrier resin and anadditive package comprising (B) an acidic condensation catalyst; wherein(A) is 50 to 99 weight percent (wt %) and the additive package is from 1to 50 wt % of total weight (100.00 wt %) of the additive masterbatchcomposition; wherein the (A) semi-crystalline polyolefin carrier resinhas a crystallinity of 50 to <100 wt % and consists essentially of anyone of limitations (i) to (vi): (i) a semi-crystalline medium densitypolyethylene; (ii) a semi-crystalline high density polyethylene; (iii) asemi-crystalline polypropylene; (iv) a semi-crystallineethylene/propylene copolymer; (v) a semi-crystallinepoly(ethylene-co-alpha-olefin) copolymer; and (vi) a combination of anytwo or more of (i), (ii) and (v); and wherein the (A) semi-crystallinepolyolefin carrier resin and is free of any carrier resin other than the(A) semi-crystalline polyolefin carrier resin.
 2. The additivemasterbatch composition of claim 1 wherein the (A) semi-crystallinepolyolefin carrier resin has (i) a density of at least 0.925 g/cm³ andis a polyethylene or a density of 0.89 to 0.90 g/cm³ and is apolypropylene; (ii) a crystallinity of at least 50 wt % and is apolyethylene; (iii) a melt flow index (MFI) of 0.1 to 20 grams per 10minutes (g/10 min.) at 190° C./2.16 kg load and is a polyethylene or amelt flow rate (MFR) of 0.5 to 50 g/10 min at 230 C./2.16 kg load and isa polypropylene; (iv) a molecular weight distribution (MWD) that ismonomodal; (v) a MWD that is bimodal; (vi) both (i) and (ii); (vii) both(i) and (iii); (viii) both (ii) and (iii); (ix) both (iv) and at leastone of (i) to (iii); or (x) both (v) and at least one of (i) to (iii).3. The additive masterbatch composition of claim 1 wherein the (B)acidic condensation catalyst is (i an organophosphonic acid or ahydrogen halide; (ii) an organosulfonic acid; (iii) an alkyl-substitutedarylsulfonic acid; (iv) an alkyl-substituted arylsulfonic acid whereinthere is/are 1 or 2 (C₅-C₂₀)alkyl substituent(s) and 1 aryl group thatis phenyl or naphthyl; (v) a (C₁-C₅)alkylphosphonic acid, wherein the(C₁ -C₅)alkyl is unsubstituted or substituted with one —NH₂ group; (vi)HF, HCl, or HBr; (vii) a Lewis acid; or (viii) a combination of any twoor more of (i) to (vii).
 4. The additive masterbatch composition ofclaim 1 further comprising at least one additive selected from: (C) asecondary diarylamine of formula (I): (R¹—Ar)₂NH (I), wherein each Ar isbenzene-1,4-diyl or both Ar are bonded to each other and taken togetherwith the NH of formula (I) constitute a carbazol-3,6-diyl; and each R¹is independently (C₁-C₂₀)hydrocarbyl; (D) one or two secondantioxidants, each having a structure different than formula (I) andeach other; (E) a processing aid; (F) a colorant; (G) a metaldeactivator; (H) an (unsaturated carbon-carbon bond)-free hydrolyzablesilane; (I) a corrosion inhibitor; (J) a combination of any two or moreof additives (D) to (I); and (K) a product of a reaction of (B) and (C).5. The additive masterbatch composition of claim 4 further comprisingthe (K) product of a reaction of (B) and (C), wherein: (i) the productof a reaction of (B) and (C) comprises a salt formed by an acid/basereaction of (B) and (C); (ii) the additive package further comprisesunreacted (B) but not unreacted (C); (iii) the additive package furthercomprises unreacted (C) but not unreacted (B); or (iv) the additivepackage further comprises unreacted (B) and unreacted (C).
 6. Amoisture-curable polyolefin composition comprising the additivemasterbatch composition of claim 1 and a (hydrolyzable silylgroup)-functional polyolefin prepolymer; wherein in the (hydrolyzablesilyl group)-functional polyolefin prepolymer: (i) each hydrolyzablesilyl group is independently a monovalent group of formula (II):(R²)_(m)(R³)_(3-m)Si— (II); wherein subscript m is an integer of 1, 2,or 3; each R² is independently H, HO—, (C₁-C₆)alkoxy, (C₂-C₆)carboxy,((C₁-C₆)alkyl)₂N—, (C₁-C₆)alkyl(H)C═NO—, or ((C₁-C₆)alkyl)₂C═NO—; andeach R³ is independently (C₁-C₆)alkyl or phenyl; (ii) the polyolefin ispolyethylene based, poly(ethylene-co-(C₃-C₄₀)alpha-olefin)-based, or acombination thereof; or (iii) both (i) and (ii).
 7. A method of making amoisture-curable polyolefin composition, the method comprising mixing a(hydrolyzable silyl group)-functional polyolefin prepolymer and adivided solid form of the additive masterbatch composition of claim 1 soas to give a mixture; and melting or extruding the mixture so as to makethe moisture-curable polyolefin composition.
 8. A moisture-curedpolyolefin composition that is a product of moisture curing the moisturecurable polyolefin composition of claim 6 to give the moisture-curedpolyolefin composition.
 9. A manufactured article comprising a shapedform of the moisture-cured polyolefin composition of claim
 8. 10. Acoated conductor comprising a conductive core and a polymeric layer atleast partially surrounding the conductive core, wherein at least aportion of the polymeric layer comprises the moisture-cured polyolefincomposition of claim
 8. 11. A method of conducting electricity, themethod comprising applying a voltage across the conductive core of thecoated conductor of claim 10 so as to generate a flow of electricitythrough the conductive core.